1. Field of the Invention
The present invention relates to a polysiloxane and a method of preparing the same, a silicon-containing alicyclic compound, and a radiation-sensitive resin composition containing the polysiloxane suitable for use in microfabrication utilizing radiation.
2. Description of the Background Art
A recent strong demand for high density and highly integrated LSIs accelerates miniaturization of wiring patterns.
Using short wave rays in a lithographic process is one method for miniaturizing wiring patterns. In recent years, deep ultraviolet rays typified by a KrF excimer laser (wavelength: 248 nm) or an ArF excimer laser (wavelength: 193 nm), electron beams, X rays, and the like are being used in place of ultraviolet rays such as g-line (wavelength: 436 nm), 1-line (wavelength: 365 nm), etc. Use of an F2 excimer laser (wavelength: 157 nm) is also being studied.
Novolac resins, poly(vinylphenol), and the like have been used as resin components for conventional resist compositions. However, because these resins exhibit strong absorbance at a wavelength of 193 nm due to inclusion of aromatic rings in the structure, a lithographic process by an ArF excimer laser, for example, using these resins cannot provide high accuracy corresponding to high photosensitivity, high resolution, and a high aspect ratio.
Therefore, a resin for use in a resist, transparent to a wavelength of 193 nm or less, particularly to a wavelength of 157 nm, and exhibiting excellent dry etching resistance equivalent to or better than aromatic rings has been desired. A polysiloxane is one such a polymer. R. R. Kunz at al. of the MIT have reported their research results showing excellent transparency of a polysiloxane at a wavelength of 193 nmor less, particularly at 157 nm, commenting on superiority of this polymer as a resist in a lithographic process using radiation with a wavelength of 193 nmor less (J. Photopolym. Sci. Technol., Vol. 12, No.4, 1999). Moreover, polysiloxanes are known to exhibit excellent dry etching properties. In particular, a resist containing polyorganosilsesquioxane having a ladder structure is known to possess high plasma resistance.
Several resist materials using a siloxane polymer have also been reported. For example, Japanese Patent Publication No. 323611/1993 discloses a radiation-sensitive resin composition comprising a polysiloxane having an acid-dissociable group such as a carboxylic acid group, phenol ether group, etc., on the side chain, bonded to a silicon atom via one or more carbon atoms. Japanese Patent Application Laid-open No. 160623/1996 discloses a positive tone resist using poly(2-carboxyethylsiloxane) in which the carboxyl group is protected with an acid-dissociable group such as a t-butyl group. Japanese Patent Application Laid-open No. 60733/1999 discloses a resist resin composition in which a polyorganosilsesquioxane providing an acid-decomposable ester group is used. However, resist materials using these conventional siloxane polymers containing an acid-dissociable group have not been satisfactory in producing basic properties in a resist such as transparency to radiation, resolution, developability, and the like.
Japanese Patent Publication No. 302382/1999 discloses a siloxane polymer having a non-aromatic monocyclic or polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group containing a carboxyl group on the side chain, at least part of the carboxyl group being replaced by a group unstable to an acid, and a resist material containing such a polymer. This resist material exhibits small absorbance of a KrF excimer laser (wavelength: 248 nm) or an ArF excimer laser (wavelength: 193 nm), produces fine pattern configuration, and excels in properties such as sensitivity, resolution, dry etching resistance, etc. However, even if the above-mentioned siloxane polymer is considered, there are few siloxane polymer useful as a resin component of a resist material. A new siloxane polymer which can provide a resist material effectively sensing radiation with a short wavelength, exhibiting high transparency to radiation and superior anti-dryetching properties, and excelling in basic resist properties, and a silicon compound which can produce such a siloxane polymer are important subjects of development in view of the fast advance in microprocessing technologies for semiconductors.
Therefore, an object of the present invention is to provide a novel polysiloxane useful as a resin component for a resist material effectively sensing radiation with a short wavelength, typified by a KrF excimer laser (wavelength: 248 nm), and an ArF excimer laser (wavelength: 193 nm), and an F2 excimer laser (wavelength: 157 nm), exhibiting high transparency to radiation and superior dry etching properties, and excelling in basic resist properties required for resist materials such as high sensitivity, resolution, developability, etc.; a method of preparing such a polysiloxane; a silicon-containing alicyclic compound providing this polysiloxane; and a radiation-sensitive resin composition comprising this polysiloxane.
Therefore, an object of the present invention is to provide a novel polysiloxane useful as a resin component for a resist material effectively sensing radiation with a short wavelength, typified by a KrF excimer laser (wavelength: 248 nm), and an ArF excimer laser (wavelength: 193 nm), and an F2 excimer laser (wavelength: 157 nm), exhibiting high transparency to radiation and superior dry etching properties, and excelling in basic resist properties required for resist materials such as high sensitivity, resolution, developability, etc.; a method of preparing such a polysiloxane; a silicon-containing alicyclic compound providing this polysiloxane; and a radiation-sensitive resin composition comprising this polysiloxane.
The present invention provides a polysiloxane having the structural unit (I) and/or structural unit (II) and structural unit (III), shown in the following formula (1), and having a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) in the range of 500-1,000,000 (this polysiloxane is hereinafter referred to as xe2x80x9cpolysiloxane (1)xe2x80x9d), 
wherein A1 and A2 individually represent a monovalent organic group having an acid-dissociable group which dissociates by an action of an acid; R1 represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, or a primary, secondary, or tertiary amino group; and R2 represents a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, or a primary, secondary, or tertiary amino group.
The present invention further provides a radiation-sensitive resin composition comprising: (a) a resin which comprises an alkali soluble or alkali low soluble polysiloxane copolymer, having the above structural unit (I) and/or structural unit (II) and structural unit (III), having a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) in the range of 500-1,000,000, and becoming soluble in alkali when an acid-dissociable group dissociates, and (b) a photoacid generator.
The present invention further provides a silicon-containing alicyclic compound represented by the following formula (2-A) or (2-B) (hereinafter referred to as xe2x80x9csilicon-containing alicyclic compound (2)xe2x80x9d), 
wherein R individually represents a hydrogen atom or a methyl group; R1 individually represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, or a primary, secondary, or tertiary amino group; and R3 individually represents a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, or the group of the following formula (i), 
wherein X individually represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, or a linear, branched, or cyclic alkoxyl group having 1-20 carbon atoms, and a indicates an integer of 1-10, or, when m is 0 or 1, two R3s may form a ring together with two oxygen atoms and the silicon atom; Y individually represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, a primary, secondary, or tertiary amino group, or a group xe2x95x90OR3 (wherein R3 is the same as defined above); m is an integer of 0-3; p is an integer of 3-10; and n is an integer of 0-3; the silicon atom binding with the 2 or 3 position of the uppermost bicyclo[2.2.1]heptane ring.
The present invention further provides a polysiloxane having the structural unit (I-1) and/or structural unit (II-1), shown by the following formulas, and having a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) in the range of 500-1,000,000 (this polysiloxane is hereinafter referred to as xe2x80x9cpolysiloxane (3)xe2x80x9d) 
wherein R individually represents a hydrogen atom or a methyl group, R1 represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, or a primary, secondary, ortertiary amino group, and nxe2x80x2 is an integer from 1-3, the silicon atom binding with the 2 or 3 position of the uppermost bicyclo[2.2.1]heptane ring.
The present invention further provides a silicon-containing alicyclic compound represented by the following formula (4-A) or (4-B) (hereinafter referred to as xe2x80x9csilicon-containing alicyclic compound (4)xe2x80x9d), 
wherein R individually represents a hydrogen atom or a methyl group; R1 individually represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, or a primary, secondary, or tertiary amino group; R3 individually represents a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, or the group of the following formula (i), 
wherein X individually represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, or a linear, branched, or cyclic alkoxyl group having 1-20 carbon atoms, and a indicates an integer of 1-10, or, when m is 0 or 1, two R3 s may form a ring together with two oxygen atoms and the silicon atom; Y individually represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, a primary, secondary, or tertiary amino group, or a group xe2x95x90OR3 (wherein R3 is the same as defined above); m is an integer of 0-3; p is an integer of 3-10; and n is an integer of 0-3; the silicon atom binding with the 2 or 3 position of the uppermost bicyclo[2.2.1]heptane ring.
The present invention further provides a polysiloxane having the structural unit (I-2) and/or structural unit (II-2), shown by the following formulas, and having a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) in the range of 500-1,000,000 (this polysiloxane is hereinafter referred to as xe2x80x9cpolysiloxane (5)xe2x80x9d), 
wherein R individually represent a hydrogen atom or a methyl group, R1 represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, or a primary, secondary, or tertiary amino group,
Rf represents a hydrogen atom, methyl group, or trifluoromethyl group, Z represents a hydrogen atom or a monovalent organic group dissociating hydrogen atoms with an action of an acid, and n is an integer of 0-3, the silicon atom binding with the 2 or 3 position of the uppermost bicyclo[2.2.1]heptane ring.
The present invention further provides a radiation-sensitive resin composition comprising:
(a) an alkali soluble or alkali low soluble polysiloxane comprising at least one structural unit selected from the structural unit (I-1xe2x80x2) and the structural unit (II-1xe2x80x2), shown by the following formulas, 
wherein R individually represents a hydrogen atom or a methyl group, R1 represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, or a primary, secondary, or tertiary amino group, Zxe2x80x2 represents a monovalent organic group dissociating by the action of oxygen to produce hydrogen atoms, and nxe2x80x2 is an integer from 1-3, the silicon atom binding with the 2 or 3 position of the uppermost bicyclo[2.2.1]heptane ring;
and having a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) in the range of 500-1,000,000 (hereinafter referred to as xe2x80x9cPolysiloxane (3xe2x80x2)xe2x80x9d) and an alkali soluble or alkali low soluble polysiloxane comprising at least one structural unit selected from the structural unit (I-2) and the structural unit (II-2), shown above, and having a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) in the range of 500-1,000,000, the resin becoming soluble in alkali when the acid-dissociable group dissociates; and
(b) a photoacid generator.
The present invention further provides a method of preparing a polysiloxane having the structural unit (I) and/or structural unit (II) and structural unit (III), shown above, and having a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) in the range of 500-1,000,000, the method comprising a step of polycondensing at least one component selected from the group consisting of a compound shown by the following formula (6) or a linear of cyclic oligomer prepared by partial condensation of this compound and/or at least one component selected from the group consisting of a compound shown by the following formula (7) or a linear of cyclic oligomer prepared by partial condensation of this compound, and at least one component selected from the group consisting of a compound shown by the following formula (8) or a linear of cyclic oligomer prepared by partial condensation of this compound in the presence of an acidic catalyst, 
wherein A1 and A2 individually represent a monovalent organic group having an acid-dissociable group which dissociates by an action of an acid, R1 represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, or a primary, secondary, or tertiary amino group, R2 represents a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, or a primary, secondary, or tertiary amino group, and R3 individually represents a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, or the group of the following formula (i), 
wherein X individually represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, or a linear, branched, or cyclic alkoxyl group having 1-20 carbon atoms, and a indicates an integer of 1-10.
The present invention further provides a method of preparing a polysiloxane having the structural unit (I-1) and/or structural unit (II-1), shown above, and having a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) in the range of 500-1,000,000, the method comprising a step of polycondensing at least one component selected from the group consisting of the silicon-containing alicyclic compounds having the above-described formulas (2-A) or (2-B) or a linear or cyclic oligomer prepared by partial condensation of this silicon-containing alicyclic compound in the presence of an acidic catalyst.
The present invention further provides a method of preparing a polysiloxane having the structural unit (I-2) and/or structural unit (II-2), shown above, and having a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) in the range of 500-1,000,000, the method comprising a step of polycondensing at least one component selected from the group consisting of the silicon-containing alicyclic compounds having the above-described formulas (4-A) or (4-B) or a linear or cyclic oligomer prepared by partial condensation of this silicon-containing alicyclic compound in the presence of an acidic catalyst.
Other objects, features and advantages of the invention will hereinafter become more readily apparent from the following description.
The present invention will be described in more detail below.
Polysiloxane (1)
Polysiloxane (1) has the structural unit (I) and/or structural unit (II) and structural unit (III), each having a formula shown above.
As the monovalent organic group having an acid-dissociable group dissociable by the action of an acid, represented by A1 and A2 in the structural unit (I) and/or structural unit (II), groups which dissociate in the presence of an acid to produce a carboxyl group, phenolic hydroxyl group, or alcoholic hydroxyl group, and are stable under the reaction conditions for preparing the polysiloxane (1) can be given. As preferable specific examples, the groups shown by the following formula (9) (hereinafter referred to as xe2x80x9can acid-dissociable group (xcex1)xe2x80x9d), the following formula (10) (hereinafter referred to as xe2x80x9can acid-dissociable group (xcex2)xe2x80x9d), the following formula (11) (hereinafter referred to as xe2x80x9can acid-dissociable group (xcex3)xe2x80x9d), and the like can be given. 
wherein p indicates a single bond, methylene group, difluoromethylene group, alkylene group having 2-20 carbon atoms, fluoroalkylene group having 2-20 carbon atoms, divalent aromatic group having 6-20 carbon atoms, or divalent alicyclic group having 3-20 carbon atoms, Q represents a group xe2x80x94Oxe2x80x94 or xe2x80x94COOxe2x80x94, and Zxe2x80x2 represents a monovalent organic group dissociating by the action of acid to produce hydrogen atoms. 
wherein R individually represents a hydrogen atom or a methyl group and n is an integer of 0-3, the free bonding hands binding with the 2 or 3 position of the uppermost bicyclo[2.2.1] heptane ring. 
wherein R individually represents a hydrogen atom or a methyl group, Rf represents a hydrogen atom, methyl group, or trifluoromethyl group, Zxe2x80x2 represents a monovalent organic group dissociating by the action of acid to produce hydrogen atoms, and n is an integer of 0-3, the free bonding hands binding with the 2 or 3 position of the uppermost bicyclo [2.2.1] heptane ring.
As examples of the alkylene group having 2-20 carbon atoms represented by P in the acid-dissociable group (xcex1), ethylene group, n-propylene group, 1-propylene group, n-butylene group, and the like can be given.
As examples of the fluoroalkylene group having 2-20 carbon atoms represented by P, a tetrafluoroethylene group, hexafluoro-n-propylene group, octafluoro-n-butylene group, and the like can be given.
As examples of the divalent aromatic group having 6-20 carbon atoms represented by P, a phenylene group, naphthylene group, perfluorophenylene group, perfluoronaphthylene group, and the like can be given.
As examples of the divalent alicyclic group having 3-20 carbon atoms represented by P, a divalent hydrocarbon group having a norbornene skeleton, tricyclodecane skeleton, or adamantane skeleton and a halide of such a hydrocarbon group can be given.
As the group P in the acid-dissociable group (xcex1), a single bond, methylene group, difluoromethylene group, a divalent hydrocarbon group having a norbornene skeleton, its halide derivative, a divalent hydrocarbon group having an adamantine skeleton, its halide derivative, and the like are preferable.
As examples of the monovalent organic group dissociating a hydrogen atom by the action of an acid represented by Zxe2x80x2 in the acid-dissociable group (xcex1) and acid-dissociable group (xcex3), a tertiary alkyl group, a group forming an acetal group together with the oxygen atom with which the group Zxe2x80x2 binds (hereinafter referred to as an xe2x80x9cacetal-forming groupxe2x80x9d), a substituted methyl group, 1-substituted ethyl group, 1-branched alkyl group (excluding tertiary alkyl groups), silyl group, germyl group, alkoxycarbonyl group, acyl group, cyclic acid-dissociable group, and the like can be given.
As examples of the tertiary alkyl group, a t-butyl group, 1,1-dimethylpropyl group, 1-methyl-1-ethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-ethylbutyl group, 1,1-dimethylpentyl group, 1-methyl-1-ethylpentyl group, 1,1-dimethylhexyl group, 1,1-dimethylheptyl group, 1,1-dimethyloctyl group, and the like can be given.
As examples of the acetal-forming group, a methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, 1-propoxymethyl group, n-butoxymethyl group, t-butoxymethyl group, n-pentyloxymethyl group, n-hexyloxymethyl group, cyclopentyloxymethyl group, cyclohexyloxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-i-propoxyethyl group, 1-n-butoxyethyl group, 1-t-butoxyethyl group, 1-n-pentyloxyethyl group, 1-n-hexyloxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, (cyclohexyl)(methoxy)methyl group, (cyclohexyl)(ethoxy)methyl group, (cyclohexyl)(n-propoxy)methyl group, (cyclohexyl)(i-propoxy)methyl group, (cyclohexyl) (cyclohexyloxy)methyl group, and the like can be given.
As examples of the substituted methyl group, a phenacyl group, p-bromophenacyl group, p-methoxyphenacyl group, p-methylthiophenacyl group, xcex1-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, p-bromobenzyl group, p-nitrobenzyl group, p-methoxybenzyl group, p-methylthiobenzyl group, p-ethoxybenzyl group, p-ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, 1-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, t-butoxycarbonylmethyl group, and the like can be given.
As examples of the 1-substituted ethyl group, a 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-i-propoxycarbonylethyl group, 1-n-butoxycarbonylethyl group, 1-t-butoxycarbonylethyl group, and the like can be given.
As examples of the 1-branched alkyl group, 1-propyl group, sec-butyl group, 1-methylbutyl group, and the like can be given.
As examples of the silyl group, a trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, 1-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, t-butyldimethylsilyl group, methyldi-t-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, triphenylsilyl group, and the like can be given.
As examples of the germyl group, a trimethylgermyl group, ethyldimethylgermyl group, methyldiethylgermyl group, triethylgermyl group, 1-propyldimethylgermyl group, methyldi-i-propylgermyl group, tri-i-propylgermyl group, t-butyldimethylgermyl group, methyldi-t-butylgermyl group, tri-t-butylgermyl group, phenyldimethylgermyl group, methyldiphenylgermyl group, triphenylgermyl group, and the like can be given.
As examples of the alkoxycarbonyl group, a methoxycarbonyl group, ethoxycarbonyl group, 1-propoxycarbonyl group, t-butoxycarbonyl group, and the like can be given.
As examples of the acyl group, an acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauryloyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, scucinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoyl group, sebacoyl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, campholoyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isonicotinoyl group, p-toluenesulfonyl group, mesyl group, and the like can be given.
As examples of the cyclic acid-dissociable group, an 3-oxocyclohexyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 2-oxo-4-methyl-4-tetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophene-1,1-dioxide group, and the like can be given.
As the monovalent organic group dissociating a hydrogen atom by the action of an acid represented by Zxe2x80x2 in the acid-dissociable group (xcex1) and acid-dissociable group (xcex3), a t-butyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, t-butyldimethylsilyl group, and the like are preferable.
As the group R in the acid-dissociable group (xcex2) and acid-dissociable group (xcex3), both the hydrogen atom and methyl group are preferable. n is preferably 0 or 1.
As the group Rf in the acid-dissociable group (xcex3), any of the hydrogen atom, methyl group, and trifluoromethyl group are preferable.
In polysiloxane (1), an acid-dissociable group (xcex2) is particularly preferable as the group A1, with an acid-dissociable group (xcex2) in which n is 1-3 being ideal. As the group A2, an acid-dissociable group (xcex3) is particularly preferable.
In the group R1 in the structural unit (II) and the group R2 in the structural unit (III), given as examples of the monovalent hydrocarbon groups having 1-20 carbon atoms are a linear or branched alkyl groups such as a methyl group, ethyl group, n-propyl group, 1-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, and the like; cycloalkyl groups such as a cyclobutyl group, cyclopentyl group, cyclohexyl group, and the like; aromatic hydrocarbon group such as a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, benzyl group, phenethyl group, 1-naphthyl group, 2-naphthyl group, and the like; and bridged hydrocarbon groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, adamantyl group, and the like.
Of these monovalent hydrocarbon groups, a methyl group and ethyl group are preferable.
As examples of the monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a monovalent hydrocarbon group having 1-20 carbon atoms in which one or more hydrogen atoms are replaced by one or more halogen atoms, preferably a fluorine atom, can be given. Specific examples include a trifluoromethyl group, pentafluoroethyl group, 3,3,3,2,2-pentafluoro-n-propyl group, perfluoro-n-propyl group, perfluoro-i-propyl group, and the group shown by the following formula (ii), 
wherein Rfxe2x80x2 individually represents a hydrogen atoms or fluorine atom, with at least one of the Rf""s being a fluorine atom, and b is an integer of 0-4, 2-(pentafluorophenyl) hexafluoro-n-propyl group, 3-(pentafluorophenyl) hexafluoro-n-propyl group, perfluoronorbornyl group, and the like can be given.
Among these monovalent halogenated hydrocarbon groups, a trifluoromethyl group, a pentafluoroethyl group, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 0, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 1, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 2,3-(pentafluorophenyl)hexafluoro-n-propyl group, and the like are preferable.
As examples of halogen atoms, a fluorine atom, chlorine atom, and bromine atom can be given, with a chlorine atom being particularly preferable.
Given as examples of secondary or tertiary amino groups are methylamino group, ethylamino group, n-propylamino group, i-propylamino group, n-butylamino group, cyclopentylamino group, cyclohexylamino group, phenylamino group, benzylamino group, dimethylamino group, diethylamino group, di-i-propylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, dibenzylamino group, and the like.
As the amino groups for R1 and R2, an amino group, dimethylamino group, diethylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, and the like are preferable.
As R1 in the structural unit (II) and R2 in the structural unit (III), a methyl group, ethyl group, cyclohexyl group, trifluoromethyl group, pentafluoroethyl group, perfluorophenethyl group,
3-(pentafluorophenyl) hexafluoro-n-propyl group, chlorine atom, dimethylamino group, and the like are preferable.
The structural unit (I), structural unit (II), and structural unit (III) maybe used in the polysiloxane (1) either individually or in combination of two or more.
The specific content of these structural units in the polysiloxane (1) may vary according to the types and combinations of the structural units, the application of the polysiloxane (1), and the like. A preferable specific content of each unit may be suitably determined by experiments and the like. The amount of the structural unit (I) is usually 1-95 mol %, preferably 5-80 mol %, and particularly preferably 10-60 mol % of the total amount of the structural units. The amount of the structural unit (II) is usually 95 mol % or less, preferably 0-50 mol %, and particularly preferably 0-30 mol % of the total amount of the structural units. The amount of the structural unit (III) is usually 5-95 mol %, preferably 20-95 mol %, and particularly preferably 40-90 mol % of the total amount of the structural units. The total of the structural unit (I) and the structural unit (II) is usually 1-95 mol %, preferably 5-80 mol %, and particularly preferably 10-60 mol % of the total amount of the structural units.
If the amount of the structural unit (I) is less than 1 mol %, resolution of the radiation-sensitive resin composition tends to decrease. If the amount exceeds 95 mol %, transparency tends to decrease. If the amount of the structural unit (II) is more than 95 mol %, the glass transition temperature and transparency of the resulting polymer tends to decrease. If the amount of the recurring unit (III) is less than 5 mol, transparency tends to decrease. If the amount exceeds 95 mol %, on the other hand, resolution of the radiation-sensitive resin composition tends to decrease. If the total amount of the structural unit (I) and the structural unit (II) is less than 1 mol %, solubility of the resulting resin composition in an alkaline developer tends to decrease. If the amount exceeds 95 mol %, solubility of the resulting resin composition in an alkaline developer tends to increase. In either case, it may become difficult for the resulting radiation-sensitive resin composition to forma highly accurate resist pattern shape.
The amount of the structural units other than structural units (I)-(III) is usually 90 mol % or less, and preferably 95 mol % or less of the total amount of all structural units.
The total amount of bi-functional structural units in the polycondensation reaction is usually 0-100 mol %, and preferably 1-100 mol %. The total amount of tri-functional structural units in the polycondensation reaction is usually 1-100 mol %, and preferably 2-100 mol %. The total amount of tetra-functional structural units in the polycondensation reaction is usually 90 mol % or less, and preferably 50 mol % or less.
Usually, polysiloxane (1) has a ladder structure as part of the molecular structure. The ladder structure is principally introduced by a raw material having tri- or greater functional structure with respect to the polycondensation reaction.
A typical ladder structure in polysiloxane (1) has a structural unit in which two or more of the recurring units (IV) to (VI) shown in the following formula (12) are combined together. 
wherein A1 and R2 are the same as previously defined in the above formula (1).
The polystyrene-reduced weight average molecular weight (hereinafter referred to as xe2x80x9cMwxe2x80x9d) of the polysiloxane (1) determined by gel permeation chromatography (GPC)is 500-1,000,000, preferably 500-500,000, and particularly preferably 1,000-100,000. If the Mw is less than 500, the glass transition temperature of the resulting polymer tends to decrease. If the Mw exceeds 1,000,000, on the other hand, solubility of the resulting polymer in solvents tends to decrease.
The glass transition temperature (Tg) of polysiloxane (1) is usually from xe2x88x9250 to 500xc2x0 C., and preferably from 0 to 300xc2x0 C. If the glass transition temperature (Tg) of polysiloxane (1) is less than xe2x88x9250xc2x0 C., pattern formation using the resulting radiation-sensitive resin composition tends to be difficult. If more than 500xc2x0 C., solubility of the polymer in solvents tends to decrease.
Polysiloxane (1) is usually insoluble or scarcely soluble in alkali, but becomes alkali-soluble when the acid-dissociable group dissociates. Thus, the polymer is particularly useful as an acid-dissociable group-containing resin component in radiation-sensitive resin compositions for microprocessing using various types of radiation such as deep ultraviolet radiation, electron beams, and X-rays.
Polysiloxane (1) is also useful as a material for fabricating formed articles and films, and as laminating materials, components for coating compositions, and the like.
Silicon-containing Alicyclic Compound (2)
In the silicon-containing alicyclic compound (2), as examples of the monovalent hydrocarbon group having 1-20 carbon atoms, monovalent halogenated hydrocarbon group having 1-20 carbon atoms, halogen atom, or primary, secondary, or tertiary amino group represented by R1, the corresponding groups previously mentioned in connection with the group R1 in the structural unit (II) of the polysiloxane (1) can be given.
A methyl group, ethyl group, cyclopentyl group, cyclohexyl group, norbornyl group, tetracyclodecanyl group, and the like can be given as preferable monovalent hydrocarbon groups having 1-20 carbon atoms represented by R1. Given as examples of preferable monovalent halogenated hydrocarbon groups having 1-20 carbon atoms represented by R1 are a trifluoromethyl group, pentafluoroethyl group, 3,3,3,2,2-pentafluoro-n-propyl group, pentafluorophenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluoro phenyl group, 2,6-difluorophenyl group, 3,4-difluoro phenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is, a group of the formula (ii) in which 5 Rf s are fluorine atoms and b is 2, and the like. A chlorine atom is preferable as a halogen atom represented by R1, and an amino group, dimethylamino group, diethylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, and the like are preferable as amino groups represented by R1.
Particularly preferable groups represented by R1 in the silicon-containing alicyclic compound (2) are a methyl group, ethyl group, cyclohexyl group, phenyl group, pentafluorophenyl group, chlorine atom, dimethylamino group, and the like.
As examples of the monovalent hydrocarbon group having 1-20 carbon atoms and monovalent halogenated hydrocarbon group having 1-20 carbon atoms represented by R3, the corresponding groups previously mentioned in connection with the group R1 in the structural unit (II) of the polysiloxane (1) can be given.
A methyl group, ethyl group, n-propyl group, 1-propyl group, and the like can be given as preferable monovalent hydrocarbon groups having 1-20 carbon atoms represented by R3. Given as examples of preferable monovalent halogenated hydrocarbon groups having 1-20 carbon atoms represented by R3 are a trifluoromethyl group, pentafluoroethyl group, 3,3,3,2,2-pentafluoro-n-propyl group, pentafluorophenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluoro phenyl group, 2,6-difluorophenyl group, 3,4-difluoro phenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 1, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 2, and the like.
As examples of the monovalent hydrocarbon group having 1-20 carbon atoms and monovalent halogenated hydrocarbon group having 1-20 carbon atoms represented by X in the formula (i), which shows an example of the group R3, the corresponding groups previously mentioned in connection with the group R1 in the structural unit (II) of the polysiloxane (1) can be given.
As examples of the linear, branched, or cyclic alkoxyl groups having 1-20 carbon atoms represented by X, a methoxy group, ethoxy group, n-propoxy group, 1-propoxy group, 1-butoxy group, sec-butoxy group, t-butoxy group, cyclopentyloxy group, cyclohexyloxy group, and the like can be given.
Particularly preferable groups for the group X in the formula (i) are a methyl group, phenyl group, methoxy group, and the like, a in the formula (i) is preferably 1-5.
As examples of the hydrocarbon group having 1-20 carbon atoms, halogenated hydrocarbon group having 1-20 carbon atoms, halogen atom, or primary, secondary, or tertiary amino group represented by Y, the corresponding groups previously mentioned in connection with the group R1 in the structural unit (II) of the polysiloxane (1) can be given.
Particularly preferable groups represented by R3 in the silicon-containing alicyclic compound (2) are a methyl group, ethyl group, t-butyl group, trimethylsilyl group, and the like.
As the group R in the silicon-containing alicyclic compound (2), both the hydrogen atom and methyl group are preferable. A preferable integer for m and n is 0 or 1.
The compounds shown by the following formulas (2-1) to (2-92) (wherein Me indicates a methyl group) can be given as preferable examples of the silicon-containing alicyclic compound (2): 
Of the above silicon-containing alicyclic compound (2), compounds shown by the formulas (2xe2x80x942), (2-3), (2-5), (2-6), (2-8), (2-9), (2-10), (2-11), and (2-12) are particularly preferable.
The silicon-containing alicyclic compound (2) of the above formula (2-A) is very useful as a raw material for producing the polysiloxane (3) having an acid-dissociable group, when the total number of the halogen atom for R1 and the group xe2x80x94OR3 in the formula (2-A) is two or three, or when min the formula (2-A) is 0 or 1. The other silicon-containing alicyclic compounds (2), i.e. those having the formula (2-A) wherein the total number of the halogen atom for R1 and the group xe2x80x94OR3 is one, or m is 2, or those having the above the formula (2-B), or their hydrolysis products, may also be used in the polycondensation reaction to adjust the molecular weight or molecular structure of polysiloxane (3).
The silicon-containing alicyclic compound (2) is also useful as a raw material for producing common polysiloxane resins and other silicon-containing alicyclic compounds having similar norbornane-type cyclic structure.
Polysiloxane (3)
Polysiloxane (3) has the above structural unit (I-1) or structural unit (II-1), or both.
As examples of the monovalent hydrocarbon group having 1-20 carbon atoms, monovalent halogenated hydrocarbon group having 1-20 carbon atoms, halogen atom, or secondary or tertiary amino group represented by R1 in the structural unit (II-1), the corresponding groups previously mentioned in connection with the group R1 in the structural unit (II) of the polysiloxane (1) can be given.
A methyl group, ethyl group, cyclopentyl group, cyclohexyl group, norbornyl group, tetracyclodecanyl group, and the like can be given as preferable monovalent hydrocarbon groups having 1-20 carbon atoms represented by R1 in the structural unit (II-1) Given as examples of preferable halogenated hydrocarbon groups having 1-20 carbon atoms represented by R1 are a trifluoromethyl group, pentafluoroethyl group, 3,3,3,2,2-pentafluoro-n-propyl group, pentafluorophenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluoro phenyl group, 2,6-difluorophenyl group, 3,4-difluoro phenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 1, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 2, and the like. A chlorine atom is a preferable halogen represented by R1, and an amino group, dimethylamino group, diethylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, and the like are preferable amino groups represented by R1.
Particularly preferable groups represented by R1 in the structural unit (II-1) are a methyl group, ethyl group, cyclopentyl group, cyclohexyl group, phenyl group, pentafluorophenyl group, chlorine atom, dimethylamino group, and the like.
As the group R in the structural unit (I-1) and structural unit (II-1) of the polysiloxane (3), both the hydrogen atom and methyl group are preferable. One is a preferable integer for nxe2x80x2. The nxe2x80x2 in the structural unit (I-1) and nxe2x80x2 in the structural unit (II-1) may be either the same or different.
The structural unit shown by the following formula (I-1-1) can be given as a specific example of the structural unit (I-1). 
The structural units shown by the following formulas (II-1-1) to (II-1-4) can be given as specific examples of the structural unit (II-1). 
In the polysiloxane (3), the t-butoxycarbonyl group in the structural units (1xe2x80x941) and (1xe2x80x941) is an acid-dissociable group which dissociates in the presence of an acid and produces a carboxyl group.
The structural unit (I-1) and the structural unit (II-1) may be used in the polysiloxane (3) either individually or in combination of two or more.
The content of these structural units in the polysiloxane (3) may vary according to the types and combinations of the structural units, the application of the polysiloxane (3), and the like. A preferable specific content of each unit may be suitably determined by experiments. The amount of the structural unit (I-1) is usually 1-100 mol %, preferably 2-100 mol %, and particularly preferably 5-100 mol % of the total amount of the structural units. The amount of the structural unit (II-1) is usually 0-100 mol %, preferably 1-100 mol %, and particularly preferably 2-100 mol % of the total amount of the structural units. The total of the structural units (I-1) and (II-1) is usually 1-100 mol %, preferably 2-100 mol %, and particularly preferably 5-100 mol % of the total amount of the structural units.
If the amount of the structural unit (I-1) is less than 1 mol %, resolution of the resulting radiation-sensitive resin composition tends to decrease. If the total amount of the structural unit (I-1) and structural unit (II-1) is less than 1 mol %, the resulting radiation-sensitive resin composition may have poor solubility in an alkaline developer.
The amount of the structural units other than structural units (I-1) and (II-1) is usually 99 mol % or less, and preferably 95 mol % or less, of the total amount of structural units.
The total amount of bi-functional structural units in the polycondensation reaction is usually 0-100 mol %, and preferably 1-100 mol %. The total amount of tri-functional structural units in the polycondensation reaction is usually 1-100 mol %, and preferably 2-100 mol %. The total amount of tetra-functional structural units in the polycondensation reaction is usually 98 mol % or less, and preferably 95 mol % or less.
Usually, polysiloxane (3) has a ladder structure as part of the molecular structure. The ladder structure is principally introduced by a raw material having tri- or greater functional structure with respect to the polycondensation reaction.
Mw of Polysiloxane (3) is usually 500-1,000,000, preferably 500-500,000, and particularly preferably 1,000-100,000. If the Mw is less than 500, the glass transition temperature of the resulting polymer tends to decrease. If the Mw exceeds 1,000,000, solubility of the polymer in solvents tends to decrease.
The glass transition temperature (Tg) of polysiloxane (3) is usually from xe2x88x9250 to 500xc2x0 C., and preferably from 0 to 300xc2x0 C. If the glass transition temperature (Tg) of polysiloxane (3) less than xe2x88x9250xc2x0 C., pattern formation using the resulting radiation-sensitive resin composition may be difficult. If more than 500xc2x0 C., solubility of the polymer in solvents tends to decrease.
Polysiloxane (3) is usually insoluble or scarcely soluble in alkali, but becomes alkali-soluble when the acid-dissociable group dissociates in the presence of an acid. Thus, the polymer is particularly useful as an acid-dissociable group-containing resin component in radiation-sensitive resin compositions for microprocessing using various types of radiation such as deep ultraviolet radiation, electron beams, and X-rays.
Polysiloxane (3) is also useful as a material for fabricating formed articles and films, and as laminating materials, components for coating compositions, and the like.
Silicon-containing Alicyclic Compound (4)
In the silicon-containing alicyclic compound (4), as examples of the monovalent hydrocarbon group having 1-20 carbon atoms, monovalent halogenated hydrocarbon group having 1-20 carbon atoms, halogen atom, or secondary or tertiary amino group represented by R1, the corresponding groups previously mentioned in connection with the group R1 in the structural unit (II) of the polysiloxane (1) can be given.
A methyl group, ethyl group, cyclopentyl group, cyclohexyl group, norbornyl group, tetracyclodecanyl group, and the like can be given as preferable monovalent hydrocarbon groups having 1-20 carbon atoms represented by R1. Given as examples of preferable halogenated hydrocarbon groups having 1-20 carbon atoms represented by R1 are a trifluoromethyl group, pentafluoroethyl group, 3,3,3,2,2-pentafluoro-n-propyl group, pentafluorophenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluoro phenyl group, 2,6-difluorophenyl group, 3,4-difluoro phenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 1, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 2, and the like. A chlorine atom is a preferable halogen represented by R1, and an amino group, dimethylamino group, diethylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, and the like are preferable amino groups represented by R1.
Particularly preferable groups represented by R1 in the silicon containing alicyclic compound (4) are a methyl group, ethyl group, cyclohexyl group, phenyl group, pentafluorophenyl group, chlorine atom, dimethylamino group, and the like.
As examples of the monovalent hydrocarbon group having 1-20 carbon atoms and monovalent halogenated hydrocarbon group having 1-20 carbon atoms represented by R3, the corresponding groups previously mentioned in connection with the group R1 in the structural unit (II) of the polysiloxane (1) can be given.
A methyl group, ethyl group, n-propyl group, 1-propyl group, and the like can be given as preferable monovalent hydrocarbon groups having 1-20 carbon atoms represented by R3. Given as examples of preferable halogenated hydrocarbon groups having 1-20 carbon atoms represented by R3 are a trifluoromethyl group, pentafluoroethyl group, 3,3,3,2,2-pentafluoro-n-propyl group, pentafluorophenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluoro phenyl group, 2,6-difluorophenyl group, 3,4-difluoro phenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 1, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 2, and the like.
As the group represented by the formula (i) in R3, the corresponding groups given as examples relating to R3 of the silicon-containing alicyclic compound (2) can be given.
Particularly preferable groups as the group X in the formula (i) are a methyl group, phenyl group, methoxy group, and the like. The integer represented by a in the formula (i) is preferably 1 to 5.
Particularly preferable groups represented by R3 in the silicon containing alicyclic compound (4) are a methyl group, ethyl group, t-butyl group, trimethylsilyl group, and the like.
As the group R in the silicon containing alicyclic compound (4), both the hydrogen atom and methyl group are preferable. As the group Rf, a hydrogen atom, methyl group, and trifluoromethyl group are preferable. A preferable integer for m and n is 0 or 1.
As examples of the hydrocarbon group having 1-20 carbon atoms, halogenated hydrocarbon group having 1-20 carbon atoms, halogen atom, or primary, secondary, or tertiary amino group represented by Y, the corresponding groups previously mentioned in connection with the group R1 in the structural unit (II) of the polysiloxane (1) can be given.
As preferable examples of silicon containing alicyclic compound (4) in which Z is a hydrogen atom, compounds shown by the following formulas (4-1) to (4-100) can be given. In the following formulas, Rf represents a hydrogen atom, methyl group, or trifluoromethyl group, and Me indicates a methyl group. 
Of the above silicon containing alicyclic compound (4), compounds shown by the formulas (4-2), (4-3), (4-5), (4-6), (4-8), (4-9), (4-10), (4-11), and (4-12) are particularly preferable (provided that Rf in these formulas represents a trifluoromethyl group).
The following compounds can be given as preferable examples of the silicon containing alicyclic compound (4), wherein Z is a monovalent organic group dissociating hydrogen atoms by the action of an acid.
Compounds derived from the compound shown by the above formulas (4-1) to (4-100) (provided that Rf in these formulas is a hydrogen atom) by replacing the hydrogen atom in the hydroxyl group with a t-butyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, or 1-ethoxyethyl group.
Compounds derived from the compound shown by the above formulas (4-1) to (4-100) (provided that Rf in these formulas is a methyl group) by replacing the hydrogen atom in the hydroxyl group with a t-butyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, or 1-ethoxyethyl group.
Compounds derived from the compound shown by the above formulas (4-1) to (4-100) (provided that Rf in these formulas is a trifluoromethyl group) by replacing the hydrogen atom in the hydroxyl group with a t-butyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, or 1-ethoxyethyl group.
Of the above silicon containing alicyclic compound (4), wherein Z is a monovalent organic group dissociating hydrogen atoms by the action of an acid, particularly preferable compounds are the compounds derived from the compound shown by the above formulas (4-2), (4-3), (4-5), (4-6), (4-8), (4-9), (4-10), (4-11), or (4-12) (provided that Rf in these formulas represents a trifluoromethyl group)) by replacing the hydrogen atom in the hydroxyl group with a t-butyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, or 1-ethoxyethyl group.
The silicon containing alicyclic compound (4) having a hydrogen atom for the group Z is particularly useful as a raw material for synthesizing the silicon containing alicyclic compound (4), wherein Z is a monovalent organic group dissociating hydrogen atoms by the action of an acid.
The silicon containing alicyclic compound (4), in which Z is a hydrogen atom and the total number of the halogen atom for R1 and the group xe2x80x94OR3 is two or three, or the silicon containing alicyclic compound (4), in which m is 0 or 1, is very useful as a raw material for producing the alkali-soluble polysiloxane (5). The silicon containing alicyclic compounds (4), in which Z is a hydrogen atom and the total number of the halogen atom for R1 and the group xe2x80x94OR3 is one, or the silicon containing alicyclic compounds (4), in which Z is a hydrogen atom and m is 2, or the products obtained by previous hydrolysis of these compounds may also be used in the polycondensation reaction to adjust the molecular weight or molecular structure of polysiloxane (5).
In addition, the silicon-containing alicyclic compound (4) in which Z is a hydrogen atom is also useful as a raw material for producing common polysiloxane resins and other silicon-containing alicyclic compounds having similar norbornane-type cyclic structure.
The silicon-containing alicyclic compound (4) in which Z is a monovalent organic group dissociating hydrogen atoms by the action of an acid and m is 0 or 1 is very useful as a raw material for producing the polysiloxane (5) resins having an acid-dissociable group. The silicon-containing alicyclic compound (4) in which Z is a monovalent organic group dissociating hydrogen atoms by the action of an acid and m is 2, or its hydrolysis products may also be used in the polycondensation reaction to adjust the molecular weight or molecular structure of polysiloxane (5).
In addition, the silicon-containing alicyclic compound (4) in which Z is a monovalent organic group dissociating hydrogen atoms by the action of an acid is also useful as a raw material for producing common polysiloxane resins and other silicon-containing alicyclic compounds having similar norbornane-type cyclic structure.
Polysiloxane (5)
Polysiloxane (5) has the above structural unit (I-2) and/or structural unit (II-2) shown in the above formula (5).
As examples of the monovalent organic group dissociating hydrogen atoms by the action of an acid represented by Z in the structural unit (I-2) or structural unit (II-2), a tertiary alkyl group, a group forming an acetal group together with the oxygen atom with which the group Z binds (hereinafter referred to as an xe2x80x9cacetal-forming groupxe2x80x9d), a substituted methyl group, 1-substituted ethyl group, 1-branched alkyl group (excluding tertiary alkyl groups), silyl group, germyl group, alkoxycarbonyl group, acyl group, cyclic acid-dissociating group, and the like can be given.
As examples of the tertiary alkyl group, acetal-forming group, substituted methyl group, 1-substituted ethyl group, 1-branched alkyl group, silyl group, germyl group, alkoxycarbonyl group, acyl group, and cyclic acid-dissociating group, the corresponding groups previously given as examples of Zxe2x80x2 in the acid-dissociable group (xcex3) of polysiloxane (1) can be given.
As the group Z in the structural unit (I-2) or structural unit (II-2), a hydrogen atom, t-butyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, and the like are preferable.
The Z in the structural unit (I-2) and Z in the structural unit (II-2) may be either the same or different.
As examples of the monovalent hydrocarbon group having 1-20 carbon atoms, monovalent halogenated hydrocarbon group having 1-20 carbon atoms, halogen atom, or secondary or tertiary amino group represented by R1 in the structural unit (II-2), the corresponding groups previously mentioned in connection with the group R1 in the structural unit (II) of the polysiloxane (1) can be given.
A methyl group, ethyl group, cyclopentyl group, cyclohexyl group, norbornyl group, tetracyclodecanyl group, and the like can be given as preferable monovalent hydrocarbon groups having 1-20 carbon atoms represented by R1. Given as examples of preferable monovalent halogenated hydrocarbon groups having 1-20 carbon atoms represented by R1 are a trifluoromethyl group, pentafluoroethyl group, 3,3,3,2,2-pentafluoro-n-propyl group, pentafluorophenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluoro phenyl group, 2,6-difluorophenyl group, 3,4-difluoro phenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 1, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 2, and the like. A chlorine atom is a preferable halogen represented by R1, and an amino group, dimethylamino group, diethylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, and the like are preferable amino groups represented by R1.
Particularly preferable groups represented by R1 in the structural unit (II-2) are a methyl group, ethyl group, cyclopentyl group, cyclohexyl group, pentafluoroethyl group, chlorine atom, dimethylamino group, and the like.
As the group R in the structural unit (I-2) and structural unit (II-2) of the polysiloxane (5), both the hydrogen atom and methyl group are preferable. As the group Rf, any one of the hydrogen atom, methyl group, and trifluoromethyl group is preferable. 0 or 1 is preferable as the integer n. The Rf in the structural unit (I-2) and Rf in the structural unit (II-2) may be either the same or different. Also, n in the structural unit (I-2) and n in the structural unit (II-2) may be either the same or different, The structural units shown by the following formulas (I-2-1) to (I-2-24) can be given as specific examples of the structural unit (I-2). 
Of the above examples of structural unit (I-2), the structural units shown by the formulas (I-2-2), (I-2-3), (I-2-5), (I-2-6), (I-2-8), (I-2-9), (I-2-14), (I-2-15), (I-2-17), (I-2-18), (I-2-20), and (I-2-21) are particularly preferable.
The structural units shown by the following formulas (II-2-1) to (II-2-96) can be given as specific examples of the structural unit (II-2). 
Of the above examples of structural unit (II), the structural units shown by the formulas (II-2-14), (II-2-15), (II-2-17), (II-2-18), (II-2-20), (II-2-21), (II-2-26), (II-2-27), (II-2-29), (II-2-30), (II-2-32), (II-2-33), (II-2-62), (II-2-63), (II-2-65), (II-2-66), (II-2-68), (II-2-69), (II-2-74), (II-2-75), (II-2-77), (II-2-78), (II-2-80), and (II-2-81) are particularly preferable.
The structural unit (I-2) and the structural unit (II-2) may be used in the polysiloxane (5) either individually or in combination of two or more.
Usually, polysiloxane (5) has a ladder structure as part of the molecular structure. The ladder structure is principally introduced by a raw material having tri- or greater functional structure with respect to the polycondensation reaction.
The content of these structural units in the polysiloxane (5) may vary according to the types and combinations of the structural units, the application of the polysiloxane (5), and the like. A preferable specific content of each unit may be suitably determined by experiments. The amount of the structural unit (I-2) is usually 1-100 mol %, preferably 2-100 mol %, and particularly preferably 5-100 mol % of the total amount of the structural units. The amount of the structural unit (II-2) is usually 0-100 mol %, preferably 1-100 mol %, and particularly preferably 2-100 mol % of the total amount of the structural units. The total of the structural units (I-2) and (II-2) is usually 1-100 mol %, preferably 2-100 mol %, and particularly preferably 5-100 mol % of the total amount of the structural units.
If the amount of the structural unit (I-2) is less than 1 mol %, resolution of the resulting radiation-sensitive resin composition tends to decrease. If the total amount of the structural unit (I-2) and structural unit (II-2) is less than 1 mol %, the resulting radiation-sensitive resin composition may have poor solubility in an alkaline developer.
The amount of the structural units other than structural units (I-1) and (II-1) is usually 99 mol % or less, and preferably 95 mol % or less, of the total amount of structural units.
The total amount of bi-functional structural units in the polycondensation reaction is usually 0-100 mol %, and preferably 1-100 mol %. The total amount of tri-functional structural units in the polycondensation reaction is usually 1-100 mol %, and preferably 2-100 mol %. The total amount of tetra-functional structural units in the polycondensation reaction is usually 98 mol % or less, and preferably 95 mol % or less.
Mw of Polysiloxane (5) is usually 500-1,000,000, preferably 500-500,000, and particularly preferably 800-100,000. If the Mw is less than 500, the glass transition temperature of the resulting polymer tends to decrease. If the Mw exceeds 1,000,000, solubility of the polymer in solvents tends to decrease.
The glass transition temperature (Tg) of polysiloxane (5) is usually from xe2x88x9250 to 500xc2x0 C., and preferably from 0 to 300xc2x0 C. If the glass transition temperature (Tg) of polysiloxane (5) less than xe2x88x9250xc2x0 C., pattern formation using the resulting radiation-sensitive resin composition may be difficult. If more than 500xc2x0 C., solubility of the polymer in solvents tends to decrease.
The polysiloxane (5) having a hydrogen atom for Z is usually soluble in alkali and very useful as an alkali-soluble component in radiation-sensitive resin compositions for microprocessing using various types of radiation such as deep ultraviolet radiation, electron beams, and X-rays.
The polysiloxane (5) having a hydrogen atom for the group Z is also useful as a raw material for synthesizing the polysiloxane (5), wherein Z is a monovalent organic group dissociating hydrogen atoms by the action of an acid.
Polysiloxane (5), in which Z is a monovalent organic group dissociating hydrogen atoms by the action of an acid, is usually insoluble or scarcely soluble in alkali, but becomes alkali-soluble when the acid-dissociable group dissociates. Thus, the polymer is particularly useful as an acid-dissociable group-containing resin component in radiation-sensitive resin compositions for microprocessing using various types of radiation such as deep ultraviolet radiation, electron beams, and X-rays.
The polysiloxane (5) is also useful as a material for fabricating formed articles and films, and as laminating materials, components for coating compositions, and the like.
Synthesis of silicon-containing alicyclic compound (2) and silicon-containing alicyclic compound (4)
The silicon-containing alicyclic compound (2) and silicon-containing alicyclic compound (4) can be synthesized by the following method, for example.
{circle around (1)} A method of reacting a corresponding norbornene derivative and corresponding hydrosilane compound in accordance with a conventional hydrosilyl-formation reaction using a hydrosilyl-formation catalyst in the presence or absence of a suitable solvent.
This reaction is shown by the following reaction formula in the case of the silicon-containing alicyclic compound (2) having the above-described formula (2-A). 
wherein R, R1, R3, m, and n have the same meanings as defined for the corresponding symbols in the formula (2-A). As examples of the hydrosilyl-forming catalyst, a transition metal catalyst, radical reaction initiator, and the like can be given.
Examples of a transition metal catalyst used as the hydrosilyl-forming catalyst include the following compounds: platinum catalysts such as H2PtCl6, K2PtCl6, Na2PtCl6, (NH4)2PtCl6, K2PtCl4, Na2PtCl4, (NH4)2PtCl4, PtCl2, H2PtBr6, K2PtBr6, Na2PtBr6, PtBr4, K2PtBr4, PtBr2, K2PtI6, Na2PtI6, PtI4, PtI2, PtCl2(C6H5CN), PtCl2(CH3CN)2, PtCl2[P(C6H5)3]2, cis-PtCl2(styrene)2, cis-PtCl2(p-chlorostyrene)2, KPtCl3(styrene)2, (n-Bu)4NPtCl3(styrene)2 (provided that n-Bu indicates n-butyl group, hereinafter the same), the compound shown by the following formula (iii), 
trans-PtCl2(NH3)2, cis-PtCl2[P(C2H5)3]2, cis-PtCl2[P(n-Bu)3]2, [(n-Bu)4N]2PtCl6, [P(C6H5)4]2PtCl4, (n-Bu)4NPtI3(CO), [(n-Bu)4N]2-cis-PtCl2(SnCl3)2, [(CH3)4N]3Pt(SnCl3)5, [bis (triphenylphosphine)imminum], Pt(SnCl3)3[As (C2H5)3]2, (C2H5)4NPt (SnCl3)3 (1,5-cyclooctadiene), platinum-activated carbon, platinum black, etc.; palladium catalysts such as PdCl2[P(C6H5)3]2, PdCl2(1,5-cyclooctadiene), palladium-activated carbon, palladium black, etc.; rhodium catalysts such as HRh[P(C6H5)3]4, rhodium-activated carbon, etc.; iridium catalysts such as IrCl3, etc.; ruthenium catalysts such as RuCl3, etc.; cobalt catalysts such as Co2(CO) 8, etc.; nickel catalysts such as NiCl2, NiBr2, Ni(CN)2, etc.; and copper catalysts such as CuCl2, CuBr2, CuCl, CuBr, CuCN, etc.
Of these transition metal catalysts, platinum catalysts such as H2PtCl6, K2PtCl6, Na2PtCl6, K2PtCl4, Na2PtCl4, PtCl2, H2PtBr6, K2PtBr6, Na2PtBr6, K2PtBr4, and platinum-activated carbon are preferable.
These transition metal catalysts may be used either individually or in combination of two or more.
The transition metal catalysts may be added as a solution in an organic solvent such as 1-propyl alcohol.
These transition metal catalysts are usually used in the amount of 0.00001-1,000 parts by weight for 100 parts by weight of the hydrosilane compound.
As examples of the above-mentioned radical reaction initiator, benzoylperoxide, lauroylperoxide, diisopropylperoxydicarbonate, t-butylhydroperoxide, cumenehydroperoxide, di-t-butylperoxide, dicumylperoxide, azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile), azobis (4-methoxy-2,4-dimethylvaleronitrile), and the like can be given.
These radical reaction initiators may be used either individually or in combinations of two or more.
The radical reaction initiators are usually used in the amount of 0.01-1,000 parts by weight for 100 parts by weight of the hydrosilane compound.
The following solvents can be given as the solvent used in the hydrosilyl-forming reaction: aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-hexane, n-heptane, and n-octane; ethers such as benzyl ethyl ether, di-n-hexyl ether, and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; linear or branched ketones such as 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, and 2-octanone; cyclic ketones such as cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, and isophorone; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, and propylene glycol mono-t-butyl ether acetate; alkyl 2-hydroxypropionates such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, 1-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, 1-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, and t-butyl 2-hydroxypropionate; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate; alcohols such as n-propylalcohol, 1-propylalcohol, n-butylalcohol, t-butylalcohol, 1-octanol, 1-nonanol, benzyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-propyl ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol mono-n-propyl ether acetate; other esters such as ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, xcex3-butyrolactone, ethylene carbonate, propylene carbonate; and the like.
These solvents may be used either individually or in combination of two or more.
These solvents are usually used in the amount of 2,000 parts by weight or less for 100 parts by weight of the hydrosilane compound.
The hydrosilyl-forming reaction is preferably carried out in the absence of a solvent or in the presence of a solvent such as toluene, xylene, n-hexane, tetrahydrofuran, dichloro methane, or the like.
The hydrosilyl-forming reaction is also preferably carried out in a nitrogen or argon stream and under anhydrous conditions.
The hydrosilyl-forming reaction is carried out at a temperature of usually xe2x88x9250 to 300xc2x0 C., and preferably 0 to 200xc2x0 C. for usually five minutes to 1,000 hours.
Although a common hydrosilyl-forming reaction is thought to be preferably carried out usually under normal pressure or under pressure, the hydrosilyl-forming reaction for synthesizing the silicon-containing alicyclic compound (2) or silicon-containing alicyclic compound (4) can be carried out at a pressure less than the normal pressure, without requiring a special reaction vessel. This is an advantage of this reaction.
In this hydrosilyl-forming reaction, the compounds in which the silicon atom, shown in formulas (2-A), (2-B), (4-A), or (4-B), binds at the 2 or 3 position of the uppermost bicyclo[2.2.1]heptane ring are produced at the same time. The mixture can be used as is as a raw material for producing the polysiloxane (3) and polysiloxane (5), for example. As required, the two compounds may be separated by a suitable means such as distillation, recrystallization, liquid chromatography, gas chromatography, and the like.
The compound (2) of the above formula (2-B) or (4-B) can be synthesized by a conventional condensation reaction of a compound derived from the compound having the total number of the group R1 as a halogen atom and the group xe2x80x94OR3 in the formula (2-A) or (4-A) of two or three, by introducing a silanol group by hydrolyzing the halogen atom or at least part of the group xe2x80x94OR3, in the presence of an acid catalyst or alkaline catalyst.
The silicon-containing alicyclic compound (4) in which Z is a monovalent organic group dissociating hydrogen atoms by the action of an acid can be synthesized from the silicon-containing alicyclic compound (4) in which Z is a hydrogen atom by replacing the hydrogen atom of the hydroxyl group of this compound with a monovalent organic group dissociating hydrogen atoms by the action of an acid.
More particularly, the above method can be carried out as follows, for example.
{circle around (2)} When Z is a t-butoxycarbonyl group, a method of esterifying the hydroxyl group in the raw material with di-t-butyl carbonate in the presence of a catalytic amount of 4-dimethylaminopyridine.
{circle around (3)} When Z is a tetrahydropyranyl group, a method of effecting an addition reaction to the hydroxyl group in the raw material with 2,3-dihydro-4H-pyrane according to a conventional method.
{circle around (4)} When Z is an acetal group such as a 1-alkoxyethyl group, a method of effecting an addition reaction to the hydroxyl group in the raw material with a corresponding alkylvinyl ether according to a conventional method.
The above methods {circle around (2)} to {circle around (4)} can be carried out either using a suitable solvent or without using a solvent. The solvents previously given in the description relating to the method {circle around (1)} can be given as examples of the solvent used here. The reaction conditions, such as a reaction temperature and reaction time, are appropriately determined according to the method employed, types of reagents used, and the like.
In particular, the method {circle around (2)} can efficiently produce the silicon-containing alicyclic compound (4) in which the group Z is a monovalent organic group dissociating hydrogen atoms by the action of an acid. On the other hand, it is difficult to obtain the target compound by using a sodium hydride catalyst which is used to replace a hydroxyl group in common organic compounds with a t-butoxycarbonyl group.
Preparation of polysiloxane (1)
Polysiloxane (1) can be prepared by a method comprising a step of polycondensing at least one component selected from the group consisting of a compound shown by the above-described formula (6) (hereinafter referred to as xe2x80x9csilane compound (6)xe2x80x9d) or a linear of cyclic oligomer prepared by partial condensation of the silane compound (6) and/or at least one component selected from the group consisting of a compound shown by the above-described formula (7) (hereinafter referred to as xe2x80x9csilane compound (7)xe2x80x9d) or a linear of cyclic oligomer prepared by partial condensation of the silane compound (7), and at least one component selected from the group consisting of a compound shown by the above-described formula (8) (hereinafter referred to as xe2x80x9csilane compound (8)xe2x80x9d) or a linear of cyclic oligomer prepared by partial condensation of the silane compound (8) in the presence of an acidic catalyst, according to a conventional method, using or without using a solvent, in the presence of an acidic catalyst or a basic catalyst. The process preferably includes a polycondensation reaction step using an acidic catalyst.
Here, xe2x80x9cthe linear of cyclic oligomer prepared by partial condensation of the silane compound (6)xe2x80x9d, xe2x80x9cthe linear of cyclic oligomer prepared by partial condensation of the silane compound (7)xe2x80x9d, and xe2x80x9cthe linear of cyclic oligomer prepared by partial condensation of the silane compound (8)xe2x80x9d denote oligomers of usually 2-10 molecules, preferably 2-5 molecules, in the case of linear oligomers, and usually 3-10 molecules, preferably 3-5 molecules, in the case of the cyclic oligomers, each oligomer being formed by the condensation of the Sixe2x80x94OR3 groups in the silane compounds.
In the formula (6), A1 is the same as defined for the above formula (1). As examples of the monovalent hydrocarbon group having 1-20 carbon atoms and monovalent halogenated hydrocarbon group having 1-20 carbon atoms represented by R3, the corresponding groups previously mentioned in connection with the group R1 in the structural unit (II) of the polysiloxane (1) can be given. As the group represented by the formula (i), the groups corresponding to R3 of the silicon-containing alicyclic compound (2) can be given, for example.
In the formula (7), A2 and R1 are respectively the same as those defined in the above formula (1).
As examples of the monovalent hydrocarbon group having 1-20 carbon atoms and monovalent halogenated hydrocarbon group having 1-20 carbon atoms represented by R3, the corresponding groups previously mentioned in connection with the group R1 in the structural unit (II) of the polysiloxane (1) can be given. As the group represented by the formula (i), the groups corresponding to R3 of the silicon-containing alicyclic compound (2) can be given, for example.
In the formula (8), R2 is the same as defined for the above formula (1). As examples of the monovalent hydrocarbon group having 1-20 carbon atoms and monovalent halogenated hydrocarbon group having 1-20 carbon atoms represented by R3, the corresponding groups previously mentioned in connection with the group R1 in the structural unit (II) of the polysiloxane (1) can be given. As the group represented by the formula (i), the groups corresponding to R3 of the silicon-containing alicyclic compound (2) can be given, for example.
In the formulas (6) to (8), given as examples of preferable monovalent hydrocarbon groups having 1-20 carbon atoms represented by R3 are a methyl group, ethyl group, n-propyl group, i-propyl group, and the like; and as examples of preferable halogenated hydrocarbon groups having 1-20 carbon atoms represented by R3 are a trifluoromethyl group, pentafluoroethyl group, 3,3,3,2,2-pentafluoro-n-propyl group, pentafluorophenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 1, a group of the formula (ii) in which 5 Rf""s are fluorine atoms and b is 2, and the like.
As examples of the linear, branched, or cyclic alkoxyl groups having 1-20 carbon atoms represented by X in the formula (i), which represents the group R3, a methoxy group, ethoxy group, n-propoxy group, 1-propoxy group, n-butoxy group, 1-butoxy group, sec-butoxy group, t-butoxy group, cyclopentyloxy group, cyclohexyloxy group, and the like can be given. Particularly preferable groups are a methyl group, phenyl group, methoxy group, and the like, a is preferably an integer of 1-5.
Particularly preferable groups represented by R3 in the formulas (6), (7), and (8) are a methyl group, ethyl group, t-butyl group, trimethylsilyl group, and the like.
In preparing the polysiloxane (1), the silane compounds (6), (7), and (8) may be used either individually or in combination of two or more.
As examples of the inorganic acids among the above-mentioned acidic catalysts, hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, titanium tetrachloride, zinc chloride, and aluminum chloride can be given. As examples of organic acids, formic acid, acetic acid, n-propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, acetic anhydride, maleic anhydride, citric acid, benzenesulfonic acid, p-toluenesulfonic acid, and methanesulfonic acid can be given.
Of these acidic catalysts, hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, acetic anhydride, and maleic anhydride are particularly preferable.
These acidic catalysts may be used either individually or in combination of two or more.
The acidic catalysts are usually used in the amount of 0.01-10,000 parts by weight, preferably 0.1xcx9c10, for 100 parts by weight of the silane compound.
As examples of inorganic bases among the above basic catalysts, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, and potassium carbonate can be given.
The following compounds can be given as examples of organic bases: linear, branched, or cyclic monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonyamine, n-decylamine, and cyclohexylamine; linear, branched, or cyclic dialkylamines such as di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, and dicyclohexylamine; linear, branched, or cyclic trialkylamines such as triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-N-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, and tricyclohexylamine; aromatic amines such as aniline, N-methylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, and naphthylamine; aromatic diamines such as N,N,Nxe2x80x2,Nxe2x80x2-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4xe2x80x2-diaminodiphenylmethane, 4,4xe2x80x2-diaminodiphenyl ether, 4,4xe2x80x2-diaminobenzophenone, 4,4xe2x80x2-diaminodiphenylamine, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane, 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane, 1,4-bis[1-(4-aminophenyl)-1-methylethyl]benzene, and 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene; imidazoles such as imidazole, benzimidazole, 4-methylimidazole, and 4-methyl-2-phenylimidazole; pyridines such as pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, and acridine; piperazines such as piperazine and 1-(2-hydroxyethyl)piperazine; as well as other nitrogen-containing heterocyclic compounds such as pyrazine, pyrazole, pyridazine, quinoxaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, and 1,4-diazabicyclo[2.2.2]octane.
Of these basic catalysts, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and the like are preferable.
These basic catalysts may be used either individually or in combination of two or more. The basic catalysts are usually used in the amount of 0.01-10,000 parts by weight, preferably 0.1xcx9c10, for 100 parts by weight of the silane compound.
The use of an acidic catalyst in the preparation of polysiloxane (1) ensures a uniform and rapid polycondensation reaction accompanying hydrolysis, reducing the amount of hydrolysable groups in the raw material left unreacted in the resulting polymer, thereby minimizing absorption of radiation by the hydrolysable groups. Therefore, polycondensation under acidic conditions is more advantageous than polycondensation under basic conditions also with regard to the radiation transmittance in the wavelength range less than 193 nm.
Another advantage of carrying out the polycondensation under acidic conditions is that the resulting polysiloxane (1) has a narrow molecular weight distribution. The radiation-sensitive resin composition prepared from such a polysiloxane (1) is less susceptible to a negative-tone reaction when exposed to radiation having a wavelength less than the deep ultraviolet region, whereby the resin composition exhibits improved adhesion properties to resist pattern substrates. Furthermore, resist patterns with a fine and excellent configuration can be obtained also in the case where the resist is developed using a common developer due to homogeneous dissolution of resist films. This is a feature manifestly observed when the resist is exposed to radiation with a wavelength of 193 nm or less.
Moreover, the polycondensation of a raw material silane compound under acidic conditions, followed by the addition of a basic catalyst to continue the reaction under basic conditions increases the degree of polymerization of the resulting polysiloxane (1). Such a polysiloxane has a higher Tg and exhibits more excellent characteristics as a result of increased crosslinking. However, when the polysiloxane (1) is used as a material for the radiation-sensitive resin composition, which is discussed later in this specification, it should be noted that the problem as to which type of polysiloxane (1), i.e. the polysiloxane (1) obtained only by the polycondensation under acidic conditions and the polysiloxane (1) obtained by the polycondensation under acidic conditions followed by basic conditions is preferred depends on the type of the radiation-sensitive resin composition.
The polycondensation reaction under acidic conditions or basic conditions is preferably carried out in an inert gas atmosphere such as nitrogen or argon, whereby an advantage of a resist less susceptible to a negative-tone reaction can be ensured when forming a resist pattern using the radiation-sensitive resin composition.
The following solvents can be given as the solvent used in the polycondensation reaction: linear or branched ketones such as 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, and 2-octanone; cyclic ketones such as cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, and isophorone; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, and propylene glycol mono-t-butyl ether acetate; alkyl 2-hydroxypropionates such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl-2-hydroxypropionate, 1-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, 1-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, and t-butyl 2-hydroxypropionate; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate; alcohols such as n-propylalcohol, 1-propylalcohol, n-butylalcohol, t-butylalcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-propyl ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol mono-n-propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; other esters such as ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, butyl 3-methoxyacetate, butyl 3-methyl-3-methoxyacetate, butyl 3-methyl-3-methoxypropionate, butyl 3-methyl-3-methoxybutyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethyleneglycol monoethyl ether, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzylalcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, xcex3-butyrolactone, ethylene carbonate, propylene carbonate; and the like.
These solvents may be used either individually or in combination of two or more.
These solvents are usually used in the amount of 2,000 parts by weight or less for 100 parts by weight of all of the silane compounds.
In addition, water may be added to the reaction mixture of the polycondensation reaction. The amount of water to be added is usually 10,000 parts by weight or less for 100 parts by weight of all of the silane compounds.
Furthermore, hexamethyldisiloxane may be added to the reaction mixture of the polycondensation reaction to control the molecular weight of the polysiloxane (1) and to increase stability.
The amount of hexamethyldisiloxane added is usually 500 parts by weight or less, and preferably 50 parts by weight or less, for 100 parts by weight of all of the silane compounds. If the amount of hexamethyldisiloxane exceeds 500 parts by weight, the resulting polymer tens to have a small molecular weight and a low glass transition temperature (Tg).
The polycondensation reaction is carried out at a temperature of usually xe2x88x9250 to 300xc2x0 C., and preferably 20 to 100xc2x0 C., usually for a period of one minute to 100 hours.
In preparing the polysiloxane (1), one or more other silane compounds may be used together with the above-described silane compounds (6), (7), and (8), or their partial condensates.
As examples of the other silane compounds, a silane compound of the following formula (12) (hereinafter referred to as xe2x80x9csilane compound (12)xe2x80x9d), a silane compound of the following formula (13) (hereinafter referred to as xe2x80x9csilane compound (13)xe2x80x9d), a silane compound of the following formula (14) (hereinafter referred to as xe2x80x9csilane compound (14)xe2x80x9d), and partial condensates of these silane compounds can be given.
xe2x80x9cPartial condensatexe2x80x9d herein indicates a linear oligomer formed from 2-10, preferably 2-5, silane molecules, or a cyclic oligomer formed from 3-10, preferably 3-5, silane molecules. 
In the formulas (12)-(14), B1, B2, and B3 individually represent a hydrogen atom, hydroxyl group, halogen atom, a substituted or unsubstituted alkyl group having 1-10 carbon atoms, a substituted or unsubstituted alkoxyl group having 1-10 carbon atoms, a substituted or unsubstituted acetoxy group, substituted or unsubstituted aryl group having 6-15 carbon atoms, substituted or unsubstituted aralkyl group having 7-20 carbon atoms, or other monovalent organic groups having an oxygen atom; and R4 and R5 individually represent an alkyl group having 1-10 carbon atoms or halogenated alkyl group having 1-10 carbon atoms; provided that B1, B2 , and B3 do not include A1 in the formula (6) nor A2 in the formula (7).
As examples of the halogen atom shown by B , B2, and B3 in the formulas (12) to (14), chlorine atom, bromine atom, and iodine atom can be given.
The following groups can be given as examples of the substituted or unsubstituted alkyl group having 1-10 carbon atoms represented by the group B1, B2, or B3 methyl group, ethyl group, n-propyl group, 1-propyl group, n-butyl group, 1-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 4-hydroxycyclohexyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 4-carboxycyclohexyl group, methoxymethyl group, 2-methoxyethyl group, 3-methoxypropyl group, 4-methoxybutyl group, 4-methoxycyclohexyl group, acetoxymethyl group, 2-acetoxyethyl group, 3-acetoxypropyl group, 4-acetoxybutyl group, 4-acetoxycyclohexyl group, mercaptomethyl group, 2-mercaptoethyl group, 3-mercaptopropyl group, 4-mercaptobutyl group, 4-mercaptocyclohexyl group, cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl group, 4-cyanocyclohexyl group, 3-glycidoxypropyl group, 2-(3,4-epoxy)cyclohexyl group, 2-(3,4-epoxy)cyclohexylethyl group, and 3-morpholinopropyl group.
As examples of the substituted or unsubstituted alkoxyl group having 1-10 carbon atoms represented by B1, B2, or B3, methoxy group, ethoxy group, n-propoxy group, 1-propoxy group, n-butoxy group, 1-butoxy group, sec-butoxy group, t-butoxy group, cyclohexyloxy group, fluoromethoxy group, chloromethoxy group, 2-chloroethoxy group, 2-bromoethoxy group, 3-chloropropoxy group, 3-bromopropoxy group, 3-glycidoxypropoxy group, 4-fluorocyclohexyloxy group, and 3,4-epoxycyclohexyloxy group can be given.
As examples of the substituted or unsubstituted aceoxy group represented by B1, B2, or B3, acetoxy group, trifluoroacetoxy group, chloroacetoxy group, and bromoacetoxy group can be given.
As examples of the as substituted or unsubstituted aryl group having 6-15 carbon atoms represented by B1, B2, or B3, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xcex1-naphthyl group, xcex2-naphthyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2-carboxyphenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-acetoxyphenyl group, 3-acetoxyphenyl group, 4-acetoxyphenyl group, 2-trimethylsiloxphenyl group, 3-trimethylsiloxyphenyl group, and 4-trimethylsiloxyphenyl group can be given.
As examples of the as substituted or unsubstituted aralkyl group having 7-20 carbon atoms represented by B1, B2, or B3, benzyl group, phenethyl group, 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 4-chlorobenzyl group, 4-bromobenzyl group, 2-hydroxybenzyl group, 3-hydroxybenzyl group, 4-hydroxybenzyl group, 2-methoxybenzyl group, 3-methoxybenzyl group, 4-methoxybenzyl group, 2-acetoxybenzyl group, 3-acetoxybenzyl group, 4-acetoxybenzyl group, 2-trimethylsiloxybenzyl group, 3-trimethylsiloxybenzyl group, and 4-trimethylsiloxybenzyl group can be given.
As examples of the other oxygen-containing monovalent groups represented by B1, B2, and B3, the groups shown by the formulas (15) and (16) can be given. 
wherein Pxe2x80x2indicates a methylene group, difluoromethylene group, fluoroalkylene group having 2-20 carbon atoms, divalent aromatic group having 6-20 carbon atoms, or other divalent alicyclic groups having 3-20 carbon atoms.
As examples of the fluoroalkylene groups having 2-20 carbon atoms, divalent aromatic groups having 6-20 carbon atoms, and other divalent alicyclic groups having 3-20 carbon atoms represented by Pxe2x80x2 in the formulas (15) and (16), the same corresponding groups previously given as examples of the group P in the formula (9) can be given.
As the group Pxe2x80x2 in the formulas (15) and (16), a difluoromethylene group, a divalent hydrocarbon group having an adamantine skeleton, its halide derivative, a divalent hydrocarbon group having a norbornene skeleton, its halide derivative, and the like are preferable. The group represented by the following formula (17) is particularly preferable. 
wherein R individually represents a hydrogen atom or a methyl group, Rf represents a hydrogen atom, methyl group, or trifluoromethyl group, and n is an integer of 0-3.
As examples of the alkyl group or halogenated alkyl groups having 1-10 carbon atoms represented by R4 or R5 in the formulas (12) to (14), a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 1-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, and trifluoromethyl group can be given.
If at least one compound selected from the group consisting of the silane compounds (12)-(14) and their partial condensates is condensed together with the silane compound (6) and/or silane compound (7), or their partial condensates, the molecular weight and glass transition temperature (Tg) of the resulting polysiloxane (1) can be adequately controlled so that transparency at the wavelength of 193 nm, particularly preferable 157 nm, can be further improved.
The total amount of the silane compound (12), silane compound (13), and silane compound (14) is usually 80 wt % or less, preferably xcx9c50 wt %, and particularly preferably xcx9cwt %, for 100 wt % of all silane compounds. If this total amount exceeds 80 wt %, resolution of the resulting radiation-sensitive resin composition tends to be impaired.
Preparation of Polysiloxane (3)
Polysiloxane (3) can be prepared by the polycondensation of at least one component selected from the group consisting of the silicon-containing alicyclic compound (2) having m=0 or 1 and n=1-3 in the formula (2-A) (hereinafter referred to as xe2x80x9csilicon-containing alicyclic compound (2xe2x80x2)xe2x80x9d) and a linear or cyclic oligomer prepared by partial condensation of the silicon-containing alicyclic compound (2xe2x80x2), in the presence of an acidic catalyst or a basic catalyst using or without using a solvent in the same manner as in the case of polysiloxane (1). The process preferably includes a polycondensation reaction step using an acidic catalyst.
Here, xe2x80x9cthe linear of cyclic oligomer prepared by partial condensation of the silicon-containing alicyclic compound (2xe2x80x2)xe2x80x9d indicates oligomers of usually 2-10 molecules, preferably 2-5 molecules, in the case of linear oligomers, and usually 3-10 molecules, preferably 3-5 molecules, in the case of the cyclic oligomers, each oligomer being formed by the condensation of the Sixe2x80x94OR3 groups in the silicon-containing alicyclic compounds.
In preparing the polysiloxane (3), silicon containing alicyclic compound (2xe2x80x2) may be used either individually or in combination of two or more.
The use of an acidic catalyst in the preparation of polysiloxane (3) ensures a uniform and rapid polycondensation reaction accompanying hydrolysis, reducing the amount of hydrolysable groups in the raw material left unreacted in the resulting polymer, thereby minimizing absorption of radiation by the hydrolysable groups. Therefore, polycondensation under acidic conditions is more advantageous than polycondensation under basic conditions also with regard to the radiation transmittance in the wavelength range less than 193 nm.
Another advantage of carrying out the polycondensation under acidic conditions is that the resulting polysiloxane (3) has a narrow molecular weight distribution. The radiation-sensitive resin composition prepared from such a polysiloxane (3) is less susceptible to a negative-tone reaction when exposed to radiation having a wavelength less than the deep ultraviolet region, whereby the resin composition exhibits improved adhesion properties to resist pattern substrates. Furthermore, resist patterns with a fine and excellent configuration can be obtained also in the case where the resist is developed using a common developer due to homogeneous dissolution of resist films. This is a feature manifestly observed when the resist is exposed to radiation with a wavelength of 193 nm or less.
Moreover, in the preparation of polysiloxane (3), the polycondensation of a raw material compound under acidic conditions, followed by the addition of a basic catalyst to continue the reaction under acidic conditions increases the degree of polymerization of the resulting polysiloxane (3). Such a polysiloxane has a higher Tg and exhibits more excellent characteristics as a result of increased crosslinking. However, when the polysiloxane (3) is used as a material for the radiation-sensitive resin composition, which is discussed later in this specification, it should be noted that the problem as to which type of polysiloxane (3), i.e. the polysiloxane (3) obtained only by the polycondensation under acidic conditions and the polysiloxane (3) obtained by the polycondensation under acidic conditions followed by basic conditions is preferred depends on the type of the radiation-sensitive resin composition.
In preparing the polysiloxane (3), one or more other silane compounds may be used together with the silicon containing alicyclic compound (2xe2x80x2) or their partial condensates.
As above-described other silane compounds, the silicon-containing alicyclic compound (2) having m=0 or 1 and n=0 in the formula (2-A), silicon-containing alicyclic compound (2) having m=2 in the formula (2-A), silicon-containing alicyclic compound (4), silane compound (8), silane compound (12), silane compound (13), and silane compound (14), and their partial condensates can be given.
Use of these other silane compounds, particularly the silane compound (12) or its partial condensates, in the polycondensation reaction ensures adequate control of the molecular weight and glass transition temperature (Tg) of the resulting polysiloxane (3), whereby transparency at the wavelength of 193 nm, particularly preferable 157 nm, can be further improved. The total amount of the other silane compounds is usually 80 wt % or less, preferably 50 wt % or less, and particularly preferably 20 wt % or less of the total amount of the silicon-containing alicyclic compound (2xe2x80x2) and the other silane compounds. If this total amount exceeds 80 wt %, resolution of the resulting radiation-sensitive resin composition tends to be impaired.
Preparation of Polysiloxane (5)
Polysiloxane (5) can be prepared by the polycondensation of at least one component selected from the group consisting of the silicon-containing alicyclic compound (4) having m=0 or 1 in the formula (4-A) (hereinafter referred to as xe2x80x9csilicon-containing alicyclic compound (41) xe2x80x9d) and a linear or cyclic oligomer prepared by partial condensation of the silicon-containing alicyclic compound (2xe2x80x2), in the presence of an acidic catalyst or a basic catalyst using or without using a solvent in the same manner as in the case of polysiloxane (1) The process preferably includes a polycondensation reaction step using an acidic catalyst.
Here, xe2x80x9cthe linear of cyclic oligomer prepared by partial condensation of the silicon-containing alicyclic compound (4xe2x80x2)xe2x80x9d indicates oligomers of usually 2-10 molecules, preferably 2-5 molecules, in the case of linear oligomers, and usually 3-10 molecules, preferably 3-5 molecules, in the case of the cyclic oligomers, each oligomer being formed by the condensation of the Sixe2x80x94OR3 groups in the silicon-containing alicyclic compounds.
In preparing the polysiloxane (5), silicon containing alicyclic compound (4xe2x80x2) may be used either individually or in combination of two or more.
The use of an acidic catalyst in the preparation of polysiloxane (5) ensures a uniform and rapid polycondensation reaction accompanying hydrolysis, reducing the amount of hydrolysable groups in the raw material left unreacted in the resulting polymer, thereby minimizing absorption of radiation by the hydrolysable groups. Therefore, polycondensation under acidic conditions is more advantageous than polycondensation under basic conditions also with regard to the radiation transmittance in the wavelength range less than 193 nm.
Another advantage of carrying out the polycondensation under acidic conditions is that the resulting polysiloxane (5) has a narrow molecular weight distribution. The radiation-sensitive resin composition prepared from such a polysiloxane (5) is less susceptible to a negative-tone reaction when exposed to radiation having a wavelength less than the deep ultraviolet region, whereby the resin composition exhibits improved adhesion properties to resist pattern substrates. Furthermore, resist patterns with a fine and excellent configuration can be obtained also in the case where the resist is developed using a common developer due to homogeneous dissolution of resist films. This is a feature manifestly observed when the resist is exposed to radiation with a wavelength of 193 nm or less.
Moreover, in the preparation of polysiloxane (5), the polycondensation of a raw material compound under acidic conditions, followed by the addition of a basic catalyst to continue the reaction under acidic conditions increases the degree of polymerization of the resulting polysiloxane (5). Such a polysiloxane has a higher Tg and exhibits more excellent characteristics as a result of increased crosslinking. However, when the polysiloxane (5) is used as a material for the radiation-sensitive resin composition, which is discussed later in this specification, it should be noted that the problem as to which type of polysiloxane (5), i.e. the polysiloxane (5) obtained only by the polycondensation under acidic conditions and the polysiloxane (3) obtained by the polycondensation under acidic conditions followed by basic conditions is preferred depends on the type of the radiation-sensitive resin composition.
In preparing the polysiloxane (5), one or more other silane compounds may be used together with the silicon containing alicyclic compound (4xe2x80x2) or their partial condensates.
As the above-described other silane compounds, the silicon-containing alicyclic compound (2), the silicon-containing alicyclic compound (4) having m=2 in the formula (4-A), silane compound (8), silane compound (12), silane compound (13), and silane compound (14), and their partial condensates can be given.
Use of these other silane compounds, particularly the silane compound (12) or its partial condensates, in the polycondensation reaction ensures adequate control of the molecular weight and glass transition temperature (Tg) of the resulting polysiloxane (5), whereby transparency at the wavelength of 193 nm, particularly preferable 157 nm, can be further improved. The total amount of the other silane compounds is usually 80 wt % or less, preferably 50 wt % or less and particularly preferably 20 wt % or less of the total amount of the silicon-containing alicyclic compound (4xe2x80x2) and the other silane compounds. If this total amount exceeds 80 wt %, resolution as a resist tends to be impaired.
The silicon-containing alicyclic compound (5) in which Z is a monovalent organic group dissociating hydrogen atoms by the action of an acid can be synthesized from polysiloxane (5) in which Z is a hydrogen atom by replacing the hydrogen atom of the hydroxyl group of this compound with a monovalent organic group dissociating hydrogen atoms by the action of an acid.
More particularly, the above method can be carried out as follows, for example.
{circle around (5)} When Z is a t-butoxycarbonyl group, a method of esterifying the hydroxyl group in the raw polymer with di-t-butyl carbonate in the presence of a catalytic amount of 4-dimethylaminopyridine.
{circle around (6)} When Z is a tetrahydropyranyl group, a method of effecting an addition reaction to the hydroxyl group in the raw polymer with 2,3-dihydro-4H-pyrane according to a conventional method.
{circle around (7)} When Z is an acetal group such as a 1-alkoxyethyl group, a method of effecting an addition reaction to the hydroxyl group in the raw polymer with a corresponding alkylvinyl ether according to a conventional method.
The above methods {circle around (5)} to {circle around (7)} can be carried out usually using a suitable solvent. The solvents previously given in the description relating to the method {circle around (1)} for the preparation of the silicon containing alicyclic compound (2) and silicon containing alicyclic compound (4) can be given as examples of the solvent used here. The reaction conditions, such as a reaction temperature and reaction time, are appropriately determined according to the method employed, types of reagents used, and the like.
In particular, the method {circle around (5)} can efficiently produce the polysiloxane(4) in which the group Z is a monovalent organic group dissociating hydrogen atoms by the action of an acid. On the other hand, it is difficult to obtain the target compound by using a sodium hydride catalyst which is used to replace a hydroxyl group in common organic compounds with a t-butoxycarbonyl group.
Radiation-sensitive Resin Composition
The following compositions can be given as examples of the preferable radiation-sensitive resin composition of the present invention.
(1) A radiation-sensitive resin composition containing (a) a resin comprising an alkali insoluble or alkali low soluble polysiloxane (1), which becomes soluble in alkali when an acid-dissociable group dissociates, and (b) a photoacid generator (hereinafter referred to as xe2x80x9cradiation-sensitive resin composition (1)xe2x80x9d).
(2) A radiation-sensitive resin composition containing (a) a resin comprising an alkali insoluble or alkali low soluble polysiloxane (3xe2x80x2) and/or an alkali insoluble or alkali low soluble polysiloxane (5), which becomes soluble in alkali when an acid-dissociable group dissociates, and (b) a photoacid generator (hereinafter referred to as xe2x80x9cradiation-sensitive resin composition (2)xe2x80x9d).
The component (a) in the radiation-sensitive resin composition (1) preferably comprises a polysiloxane which comprises at least one of the structural units (I-1) and (I-2) and/or a polysiloxane which comprises at least one of the structural units (II-1) and (II-2).
The polysiloxane (3xe2x80x2) in the radiation-sensitive resin composition (3xe2x80x2) comprises the structural unit (I-1xe2x80x2) and/or the structural unit (I-2xe2x80x2) and has a Mw of 500-1,000,000. The group shown by the following formula (iii) can be given as an example of the monovalent organic group dissociating hydrogen atoms by the action of an acid represented by Zxe2x80x2 in the formula 
wherein R1 individually represents a linear or branched alkyl group having 1-4 carbon atoms or a monovalent alicyclic hydrocarbon group having 3-20 carbon atoms or a derivative thereof, or any two of R""s form in combination a divalent alicyclic hydrocarbon group having 3-20 carbon atoms or a derivative thereof, with the remaining R1 being a linear or branched alkyl group having 1-4 carbon atoms or a monovalent alicyclic hydrocarbon group having 3-20 carbon atoms or a derivative thereof.
As examples of the linear or branched alkyl group having 1-4 carbon atoms represented by R1 in the formula (iii), a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, and t-butyl group can be given.
As examples of the monovalent alicyclic hydrocarbon group having 3-20 carbon atoms and the divalent alicyclic hydrocarbon group having 3-20 carbon atoms formed by two R1 s in combination, alicyclic groups derived from a cycloalkane such as norbornane, tricyclodecane, tetracyclododecane, adamantine, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, or cyclooctane, and groups obtained by replacing hydrogen atoms on these alicyclic groups with above-mentioned one or more alkyl groups having 1-4 carbon atoms can be given.
Of these groups of the formula (iii), the group having a methyl group for R1 (corresponding to the recurring unit forming the polysiloxane (3)) is ideal.
Acid Generator (b)
The acid generator (b) used in the radiation-sensitive resin composition (1) or the radiation-sensitive resin composition (2) is a component generating an acid by exposure to radiation. The acid causes an acid-dissociable group in the resin to dissociate. As a result, an exposed part of the resist film becomes readily soluble in an alkaline developer, thereby forming a positive-tone resist pattern.
As examples of the acid generator (b), onium salts, halogen-containing compounds, diazoketone compounds, sulfone compounds, and sulfonate compounds can be given.
Examples of the acid generator (b) are given below.
Onium Salts:
As examples of onium salts, iodonium salts, sulfonium salts (including tetrahydrothiophenium salts), phosphonium salts, diazonium salts, and pyridinium salts can be given.
Specific examples of preferable onium salts include: diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium heptadecafluoro-n-octanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium naphthalenesulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate, bis(4-t-butylphenyl)iodonium heptadecafluoro-n-octanesulfonate, bis(4-t-butylphenyl)n-dodecylbenzenesulfonate, bis(4-t-butylphenyl)iodonium hexafluoroantimonate, bis(4-t-butylphenyl)iodonium naphthalenesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium heptadecafluoro-n-octanesulfonate, triphenylsulfonium pyrenesulfonate, triphenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium 10-camphorsulfonate, 4-hydroxyphenyl.phenyl.methylsulfonium, p-toluenesulfonate, cyclohexyl.2-oxocyclohexyl.methylsulfonium trifluoromethanesulfonate, cyclohexyl.2-oxocyclohexyl.methylsulfonium nonafluoro-n-butanesulfonate, cyclohexyl.2-oxocyclohexyl.methylsulfonium heptadecafluoro-n-octanesulfonate, dicyclohexyl.2-oxocyclohexylsulfonium trifluoromethanesulfonate, dicyclohexyl.2-oxocyclohexylsulfonium nonafluoro-n-butanesulfonate, dicyclohexyl.2-oxocyclohexylsulfonium heptadecafluoro-n-octanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium nonafluoro-n-butanesulfonate, 2-oxocyclohexyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-hydroxyphenyl.benzyl.methylsulfonium p-toluenesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate, 4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 4-cyano-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 4-cyano-1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 4-nitro-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 4-nitro-1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 4-methyl-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-methyl-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 4-methyl-1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-(1xe2x80x2-methoxyethoxy)-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-(2xe2x80x2-methoxyethoxy)-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-i-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-t-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-(2xe2x80x2-tetrahydrofuranyloxy)-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-(2xe2x80x2-tetrahydropyranyloxy)-1-naphthyltetrahydrothiophenium trifluoromethane sulfonate, 4-benzyl oxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1-(1xe2x80x2-naphthylacetomethyltetrahydrothiophenium trifluoromethane sulfonate, 4-n-butoxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate.
Halogen-containing Compounds:
As examples of halogen-containing compounds, haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and the like can be given.
As specific examples of preferable halogen-containing compounds, (trichloromethyl)-s-triazine derivatives such as phenylbis(trichloromethyl)-s-triazine, 4-methoxyphenylbis(trichloromethyl)-s-triazine, and 1-naphthylbis(trichloromethyl)-s-triazine, 1,1-bis (4xe2x80x2-chlorophenyl)-2,2,2-trichloroethane, and the like can be given.
Diazoketone Compounds:
As examples of diazoketone compounds, 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like can be given.
As specific examples of preferable diazoketone compounds, 1,2-naphthoquinonediazido-4-sulfonyl chloride, 1,2-naphthoquinonediazido-5-sulfonyl chloride, 1,2-naphthoquinonediazido-4-sulfonate or 1,2-naphthoquinonediazido-5-sulfonate of 2,3,4,4xe2x80x2-tetrahydroxybenzophenone, 1,2-naphthoquinonediazido-4-sulfonate or 1,2-naphthoquinonediazido-5-sulfonate of 1,1,1-tris(4xe2x80x2-hydroxyphenyl)ethane, and the like can be given.
Sulfone Compounds:
As examples of sulfone compounds, xcex2-ketosulfone, xcex2-sulfonylsulfone, xcex1-diazo compounds of these compounds, and the like can be given.
As specific examples of preferable sulfone compounds, 4-trisphenacylsulfone, mesitylphenacylsulfone, bis(phenylsulfonyl)methane, and the like can be given.
Sulfonate Compounds:
As examples of sulfonate compounds, alkyl sulfonate, alkylimide sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate, and the like can be given.
As specific examples of sulfonate compounds, benzointosylate, pyrogallol tris (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo[2.2.1]hepto-5-ene-2,3-dicar bodiimide, N-hydroxysuccinimidetrifluoromethanesulfonate, and 1,8-naphthalenedicarboxylic acid imido trifluoromethanesulfonate can be given. Of the above acid generators (b), the following compounds are preferable: diphenyliodoniumtrifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, cyclohexyl.2-oxocyclohexyl.methylsulfonium trifluoromethanesulfonate, dicyclohexyl.2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1-(1xe2x80x2-naphthylacetoiethyl)tetrahydrothiophenium trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo[2.2.1]hepto-5-ene-2,3-dicar bodiimide, N-hydroxysuccinimidetrifluoromethanesulfonate, 1,8-naphthalenedicarboxylic acid imido trifluoromethanesulfonate, and the like.
The acid generator (b) may be used either individually or in combination of two or more.
The amount of the acid generator (b) to be used in the radiation-sensitive resin composition (1) and radiation-sensitive resin composition (2) is usually 0.1-10 parts by weight, and preferably 0.5-7 parts by weight for 100 parts by weight of the resin from the viewpoint of ensuring sensitivity and developability as a resist. If the amount of the acid generator (b) is less than 0.1 part by weight, sensitivity and developability tend to decrease. If the amount exceeds 10 parts by weight, a rectangular resist pattern may not be obtained due to decreased radiation transmittance.
Additives
It is preferable to add an acid diffusion controller to the radiation-sensitive resin composition (1) and radiation-sensitive resin composition (2). The acid diffusion controller controls diffusion of an acid generated from the acid generator (b) upon exposure in the resist film to suppress unfavorable chemical reactions in the unexposed area.
The addition of such an acid diffusion controller improves storage stability of the resulting composition and resolution as a resist. Moreover, the addition of the acid diffusion controller prevents the line width of the resist pattern from changing due to changes in the post-exposure delay (PED) between exposure and development, whereby a composition with remarkably superior process stability can be obtained. As the acid diffusion controller, organic compounds containing nitrogen of which the basicity does not change during exposure or heating for forming a resist pattern are preferable.
As examples of such nitrogen-containing organic compounds, a compound shown by the following formula (18) (hereinafter called xe2x80x9cnitrogen-containing compound {circle around (1)}xe2x80x9d), 
wherein R6 individually represents a hydrogen atom, a substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted aralkyl group, a compound having two nitrogen atoms in the molecule (hereinafter referred to as xe2x80x9cnitrogen-containing compound {circle around (2)}xe2x80x9d), a polymer having three or more nitrogen atoms in the molecule (hereinafter referred to as xe2x80x9cnitrogen-containing compound {circle around (3)}xe2x80x9d), an amide group-containing compound, urea compound, nitrogen-containing heterocyclic compound, and the like can be given.
The following compounds can be given as examples of the nitrogen-containing compound {circle around (1)}: linear, branched, or cyclic monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonyamine, n-decylamine, and cyclohexylamine; linear, branched, or cyclic dialkylamines such as di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, and dicyclohexylamine; linear, branched, or cyclic trialkylamines such as triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, and tricyclohexylamine; aromatic amines such as aniline, N-methylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, and naphthylamine; and the like.
Examples of the nitrogen-containing compound {circle around (2)} include ethylenediamine, N,N,Nxe2x80x2,Nxe2x80x2-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4xe2x80x2-diaminodiphenylmethane, 4,4xe2x80x2-diaminodiphenyl ether, 4,4xe2x80x2-diaminobenzophenone, 4,4xe2x80x2-diaminodiphenylamine, 2,2-bis(4xe2x80x2-aminophenyl)propane, 2-(3xe2x80x2-aminophenyl)-2-(4xe2x80x2-aminophenyl)propane, 2-(4xe2x80x2-aminophenyl)-2-(3xe2x80x2-hydroxyphenyl)propane, 2-(4xe2x80x2-aminophenyl)-2-(4xe2x80x2-hydroxyphenyl)propane, 1,4-bis[xe2x80x2-(4xe2x80x3-aminophenyl)-1xe2x80x2-methylethyl]benzene, 1,3-bis[1xe2x80x2-(4xe2x80x3-aminophenyl)-1xe2x80x2-methylethyl]benzene, and the like.
Examples of the nitrogen-containing compounds {circle around (3)} include polyethyleneimine, polyallylamine, a polymer of 2-dimethylaminoethylacrylamide, and the like.
Examples of compounds containing an amide group include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, and the like.
Examples of the urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea, and the like. Examples of the nitrogen-containing heterocyclic compounds include: imidazoles such as imidazole, benzimidazole, 4-methylimidazole, and 4-methyl-2-phenylimidazole; pyridines such as pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, and acridine; piperazines such as piperazine, 1-(2xe2x80x2-hydroxyethyl) piperazine; pyrazine, pyrazole, pyridazine, quinoxaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane; and the like.
Of these nitrogen-containing organic compounds, the nitrogen-containing organic compounds {circle around (1)} and the nitrogen-containing heterocyclic compounds are preferable. Among the nitrogen-containing organic compounds {circle around (1)}, tri (cyclo)alkylamines are particularly preferable. Among the nitrogen-containing heterocyclic compounds, pyridines and piperazines are particularly preferable.
The acid diffusion controller may be used either individually or in combination of two or more.
The amount of the acid diffusion controller to be added to the radiation-sensitive resin composition (1) or the radiation-sensitive resin composition (2) is usually 15 parts by weight or less, preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less for 100 parts by weight of the resin. If the proportion of the acid diffusion controller exceeds 15 parts by weight, sensitivity as a resist and developability of the exposed area tend to decrease. If the amount is less than 0.001 part by weight, the pattern shape or dimensional accuracy as a resist may decrease depending on the processing conditions.
Surfactants which improve applicability, developability, or the like may be added to the radiation-sensitive resin composition (1) and the radiation-sensitive resin composition (2).
As examples of surfactants, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate; commercially available products such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), FTOP EF301, EF303, EF352 (manufactured by TOHKEM PRODUCTS CORPORATION), MEGAFAC F171, F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Fluorard FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.); and the like can be given.
These surfactants may be used either individually or in combination of two or more.
The amount of the surfactant to be added to the radiation-sensitive resin composition (1) or the radiation-sensitive resin composition (2) is usually 2 parts by weight or less for 100 parts by weight of the total amount of resin and the acid generator (b).
As other additives, halation inhibitors, adhesion promoters, storage stabilizers, anti-foaming agents, and the like can be given.
The radiation-sensitive resin composition (1) and radiation-sensitive resin composition (2) excel in dry etching resistance and possess superior basic properties as a resist such as excellent transmittance, sensitivity, resolution, and developability.
Preparation of Composition Solution
The radiation-sensitive resin composition (1) and radiation-sensitive resin composition (2) can be prepared as a composition solution by dissolving the composition in a solvent so that the total solid content is 1-25 wt %, and preferably 2-15 wt %, and filtering the composition using a filter with a pore diameter of about 0.2 xcexcm, for example.
Examples of solvents used for the preparation of the composition solution include: linear or branched ketones such as 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, and 2-octanone; cyclic ketones such as cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, and isophorone; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, and propylene glycol mono-t-butyl ether acetate; alkyl 2-hydroxypropionates such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, -propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, 1-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, and t-butyl 2-hydroxypropionate; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate; as well as other solvents such as n-propyl alcohol, 1-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, toluene, xylene, 2-hydroxy-2-methylethyl propionate, ethoxyethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, ethyla cetate, n-propyl acetate, n-butylacetate, methyl acetoacetoate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methyl pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzylacetate, ethylbenzoate, diethyloxalate, diethylmaleate, xcex3-butyrolactone, ethylene carbonate, and propylene carbonate.
These solvents may be used either individually or in combination of two or more. Among these solvents, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionates, and alkyl 3-alkoxypropionates are preferable.
Formation of Resist Patterns
A method of forming resist patterns using the radiation-sensitive resin composition (1) or the radiation-sensitive resin composition (2) will now be described.
In the radiation-sensitive resin composition (1) or radiation-sensitive resin composition (2), an acid is generated from the acid generator (b) upon exposure to radiation. The acid-dissociable group in the resin to dissociate by the action of the acid and generates a carboxyl group or hydroxyl group. As a result, solublity of the exposed part of the resist in an alkaline developer increases, whereby the exposed part is dissolved in an alkaline developer and removed to produce a positive-tone resist pattern.
A resist pattern is formed from the radiation-sensitive resin composition (1) or the radiation-sensitive resin composition (2) by applying the composition solution to, for example, substrates such as a silicon wafer or a wafer coated with aluminum using an appropriate application method such as rotational coating, cast coating, and roll coating to form a resist film. The resist film is then optionally pre-baked (hereinafter called xe2x80x9cPBxe2x80x9d) and exposed to form a predetermined resist pattern. An F2 excimer laser (wavelength: 157 nm), ArF excimer laser (wavelength: 193 nm), and KrF excimer laser (wavelength: 248 nm) are preferable as radiation used for exposure.
In the present invention, it is preferable to perform post-exposure bake (hereinafter called xe2x80x9cPEBxe2x80x9d) after exposure. The PEB ensures a smooth acid dissociation reaction from the resin (a). The heating temperature for PEB is usually 30-200xc2x0 C., and preferably 50-170xc2x0 C., although the heating conditions vary depending on the composition of the resist.
In order to fully bring out latent capability of the radiation-sensitive resin composition (1) and the radiation-sensitive resin composition (2), an organic or inorganic anti-reflection film may be formed on a substrate as disclosed in Japanese Patent Publication No. 12452/1994, for example. Moreover, a protection film may be formed on the resist film as disclosed in Japanese Patent Publication No. 188598/1993 or the like in order to prevent the effects of basic impurities or the like in an environmental atmosphere. These techniques may be employed in combination.
The exposed resist film is then developed to form a predetermined resist pattern.
As examples of a developer used for development, it is preferable to use an alkaline aqueous solution prepared by dissolving at least one of alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diaza bicyclo-[4.3.0]-5-nonene.
The concentration of the alkaline aqueous solution is usually 10 wt % or less. If the concentration of the alkaline aqueous solution exceeds 10 wt %, an unexposed area may be dissolved in the developer.
Organic solvents or the like may be added to the developer containing an alkaline aqueous solution.
As examples of organic solvents, ketones such as acetone, 2-butanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; alcohols such as methylalcohol, ethylalcohol, n-propylalcohol, 1-propylalcohol, n-butylalcohol, t-butylalcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate, n-butyl acetate, and 1-amyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol, acetonylacetone, dimethylformamide; and the like can be given.
These organic solvents may be used either individually or in combination of two or more.
The amount of the organic solvents is preferably 100 vol % of the alkaline aqueous solution. If the amount of the organic solvents exceeds 100 vol %, an exposed area may remain undeveloped due to decreased developability.
In addition, surfactants or the like may be added to the developer containing the alkaline aqueous solution in an appropriate amount.
The resist film is generally washed with water after development using a developer containing an alkaline aqueous solution.